CN104418379A - Preparation method of anhydrous lanthanum bromide - Google Patents

Preparation method of anhydrous lanthanum bromide Download PDF

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CN104418379A
CN104418379A CN201310376639.5A CN201310376639A CN104418379A CN 104418379 A CN104418379 A CN 104418379A CN 201310376639 A CN201310376639 A CN 201310376639A CN 104418379 A CN104418379 A CN 104418379A
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brometo
amonio
anhydrous
lanthanum
porous material
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CN104418379B (en
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卢旭晨
张志敏
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/253—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification

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  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention discloses a preparation method of anhydrous lanthanum bromide, which comprises the following steps: (1) well mixing ammonium bromide with lanthana; (2) heating the mixture obtained in step (1) in closed environment with a certain leakproofness to obtain anhydrous lanthanum bromide. The method of the invention is easily available in raw materials, and low in cost; the preparation process is simple, short in flow, easy to control, high in product yield, and low in production cost; the prepared anhydrous lanthanum bromide is high in purity, and has a purity of up to 99.5%; and the preparation method can be used for preparation of lanthanum bromide scintillation crystals, and has very good industrial and commercial prospects.

Description

A kind of preparation method of anhydrous lanthanum bromide
Technical field
The present invention relates to the preparing technical field of inorganic materials, be specifically related to a kind of preparation method of anhydrous lanthanum bromide.
Background technology
With Ce 3+ion-activated lanthanum bromide crystal (LaBr 3: Ce 3+) be a kind of novel inorganic scintillation crystal that development in recent years is got up.Compared with same crystalloid, this crystal has the advantages such as higher photoyield, preferably energy resolution, faster fall time, nonlinear response be little; Compared to traditional NaI (TI) crystal, with Ce 3+ion-activated lanthanum bromide crystal has a lot of excellent character, there is industrialization and business-like feasible prospect, be expected to replace traditional NaI (TI) crystal comprehensively, thus be used widely in fields such as Medical Instruments, high-energy physics experiment research, oil well exploration and safety random checks.
The preparation of anhydrous lanthanum bromide is one of key link of above-mentioned lanthanum bromide crystal preparation.The method of the anhydrous lanthanum bromide of current preparation has following several:
(1) chemical gas phase reaction transmission method.Yang Dongmei [refers to document: Yang Dongmei, Yu Jin, Jiang Junhui, Wang Zhichang at document.Anhydrous lanthanum bromide [J] is directly prepared by lanthanum trioxide.Material and metallurgical journal, 2003,2(2): 113-114; Yang Dongmei, Yu Jin, Jiang Junhui, Wang Zhichang.Anhydrous rare earth bromide [J] is directly prepared by rare earth oxide.Rare earth, 2004,25(2): 8-9] in describe the method in detail: the high-temperature zone that the mixture of lanthanum trioxide, bromine and aluminium powder is placed in long silica tube is reacted, obtains the mixture of anhydrous lanthanum bromide and aluminum oxide.Excessive aluminium powder and bromine reaction generate Al 2br 6gas, at a certain temperature anhydrous lanthanum bromide and Al 2br 6reaction generates gas LaAl 3br 12, gas LaAl 3br 12move to cold zone and decompose in cold zone and obtain the higher anhydrous lanthanum bromide of purity.The method complex process, long reaction time (about 24 hours), products collection efficiency low (about 26.8%).
(2) hydration lanthanum bromide complexing evaporation.Sun Tongshan [refers to document: Sun Tongshan, Zhao Yuting, Wang Qian, Li Ruimei at document.The Dehydration Kinetics of hydration lanthanum bromide and studying [J] with the synthesis of Dimethyl sulfoxide coordinated compound and thermal analyses.China rare earth journal, 1994, describe the method in detail 12(3): 213-217]: first with hydration lanthanum bromide and dimethyl sulfoxide (DMSO) for both title complexs prepared by raw material, then this title complex is heated at a certain temperature and carries out dewatering to prepare anhydrous lanthanum bromide.Experimental result shows, under static atmosphere of air, in 211 ~ 312 DEG C of temperature ranges, generates anhydrous lanthanum bromide; But when temperature is increased to more than 520 DEG C, anhydrous lanthanum bromide is lanthanum oxybromide (LaOBr) by the oxygen in air and water vapour complete oxidation.The anhydrous lanthanum bromide coking property that the method obtains is poor, is easy to again absorb water in the process stored.
(3) hydration lanthanum bromide programmed temperature method prepares anhydrous lanthanum bromide.The method has a detailed description in patent CN201110344581.7, and the method is the Phosbloc of < 20ppm with chloride content, dissolves, Phosbloc and hydrobromic weight ratio 1: 1.6 with 40% Hydrogen bromide, and through concentrating, crystallization obtains LaBr 36H 2o; LaBr 36H 2o and NH 4br mixes in mixer by weight 1: 0.8, vacuumizes with water jet pump, and when vacuum tightness reaches 0.08Pa, setting heating schedule starts heating, and temperature, in room temperature ~ 410 DEG C, controls temperature-gradient method speed and soaking time, obtains anhydrous lanthanum bromide.The method requires very harsh to reaction environment, needs to ensure very high vacuum tightness, and in addition, the control of reaction process is complicated, and needs are strict controls temperature-gradient method speed and soaking time.
(4) hydration lanthanum bromide hydrogen bromide atmosphere protection evaporation.The method is carried out by hydration lanthanum bromide dewatering to prepare anhydrous lanthanum bromide under hydrogen bromide atmosphere protection.According to chemical equilibrium theory, the existence of bromize hydrogen gas can suppress the generation of hydration lanthanum bromide dehydration later stage hydrolysis reaction greatly, and hydrolysate can be converted into anhydrous lanthanum bromide again, thus ensure that the purity of the anhydrous lanthanum bromide of product.In the method, the consumption of hydrogen bromide is very large, and require higher to the erosion resistance of equipment, the parsing purification difficulty of steam-laden hydrogen bromide tail gas is high, thus causes this processing method complexity, production cost very high.
Along with the development of lanthanum bromide scintillation crystal, also day by day urgent to the demand of Materials Absolute lanthanum bromide.Because anhydrous lanthanum bromide pyrohydrolysis is extremely strong, its preparation process to oxygen in surrounding environment and water vapour content control overflow very harsh, cause current high-purity anhydrous lanthanum bromide complex manufacturing, process control difficulties is large, product cost is very high, constrains the development of lanthanum bromide scintillation crystal.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of highly purified anhydrous lanthanum bromide, the method with lanthanum trioxide and brometo de amonio for raw material, cheaper starting materials, to be easy to get, preparation technology is simple, obtained anhydrous lanthanum bromide purity is greater than 99.5%, can be used as and prepares lanthanum bromide crystal (LaBr 3: Ce 3+) raw material.
For achieving the above object, the present invention is achieved by the following technical solution:
Prepare a method for anhydrous lanthanum bromide, comprise the steps:
(1) by brometo de amonio and lanthanum trioxide Homogeneous phase mixing;
(2) step (1) gained mixture is heated under the closed environment with certain stopping property, obtain anhydrous lanthanum bromide.
In aforesaid method, as preferably, described in step (1), the mass ratio of brometo de amonio and lanthanum trioxide is greater than 1.80; Further preferably, the mass ratio of described brometo de amonio and lanthanum trioxide is 1.80 ~ 36.10:1.00; Such as, according to certain embodiments of the present invention, the mass ratio of described brometo de amonio and lanthanum trioxide is 2.00,6.00,10.00,14.00,18.00,22.00,26.00,30.00,34.00.
Still more preferably, the mass ratio of described brometo de amonio and lanthanum trioxide is 2.98 ~ 14.44:1.00; Such as, according to certain embodiments of the present invention, the mass ratio of described brometo de amonio and lanthanum trioxide is: 3.00,3.50,4.00,4.50,5.00,5.50,6.00,6.50,7.00,7.50,8.00,8.50,9.00,9.50,10.00,10.50,11.00,11.50,12.00,12.50,13.00,13.50,14.00.
In aforesaid method, " having the closed environment of certain stopping property " described in step (2) refers to the volatilization Sum decomposition that effectively can suppress brometo de amonio, and effectively can completely cut off the closed environment that the anhydrous lanthanum bromide of product contacts with water vapour with oxygen in air, this closed environment has certain stopping property.Any mode that the mixture of lanthanum trioxide and brometo de amonio can be made to be in opposing seal environment that those skilled in the art can be adopted to know, such as, be directly placed in crucible by described mixture or other has the container of certain stopping property.
Preferably, by having the closed environment of certain stopping property described in placing coverture to realize on described mixture.
Further preferably, described coverture is solid powder or porous material; Particularly, solid powder or porous material are covered in after above described mixture, then be positioned over there is certain stopping property container in.Solid powder of the present invention all can commercially availablely obtain, and is not particularly limited particle diameter.The effect of described coverture is as follows: (1) suppresses the volatilization Sum decomposition of brometo de amonio effectively, brometo de amonio can fully be reacted, the utilization ratio of raising brometo de amonio with lanthanum trioxide; (2) the contacting of oxygen and water vapour in the isolated anhydrous lanthanum bromide of reaction product and air effectively, avoids anhydrous lanthanum bromide at high temperature hydrolysis reaction to occur.
Still more preferably, described solid powder is any one or a few mixture of Repone K, sodium-chlor, bariumchloride, calcium chloride, aluminum oxide, quartz sand, magnesium oxide, lanthanum trioxide, brometo de amonio, ammonium chloride, and described porous material is ceramic porous material, silicon carbide porous material, silicon oxide porous material, silico-aluminate porous material, aluminum oxide porous material, titanium oxide porous material, zirconium white porous material, manganese oxide porous material, ferric oxide multi-porous material, phosphate cellular material, sulfide porous material; In some embodiments of the present invention, described coverture is aluminum oxide or quartz sand or Repone K or bariumchloride or porous ceramics, in other embodiments of the present invention, described coverture is the mixture of the mixture of lanthanum trioxide and brometo de amonio or the mixture of quartz sand and aluminum oxide or magnesium oxide and ammonium chloride.
Preferably, the thickness of described coverture is greater than 4mm, such as, be: 5mm, 10mm, 15mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm, 50mm.
Further preferably, the thickness of described coverture is greater than 8mm, such as, be: 9mm, 13mm, 18mm, 23mm, 28mm, 33mm, 38mm, 43mm, 48mm, 53mm.
Preferably, step is heated to be described in (2): first 250 ~ 500 DEG C of heating 1.0 ~ 4.0 hours, then 500 ~ 850 DEG C of heating 0.5 ~ 3.0 hour.
According to certain embodiments of the present invention, described Heating temperature 250 ~ 500 DEG C is such as 280 DEG C, 310 DEG C, 340 DEG C, 370 DEG C, 400 DEG C, 430 DEG C, 460 DEG C, 490 DEG C;
1.0 ~ 4.0 hours described heat-up times were such as 1.1 hours, 1.4 hours, 1.7 hours, 2.0 hours, 2.3 hours, 2.6 hours, 2.9 hours, 3.2 hours, 3.5 hours, 3.8 hours;
Described Heating temperature 500 ~ 850 DEG C is such as 510 DEG C, 540 DEG C, 570 DEG C, 600 DEG C, 630 DEG C, 660 DEG C, 690 DEG C, 720 DEG C, 750 DEG C, 780 DEG C, 810 DEG C, 840 DEG C;
0.5 ~ 3.0 hour described heat-up time was such as 0.6 hour, 0.8 hour, 1.0 hours, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2.0 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3.0 hours.
Further preferably, step is heated to be described in (2): first 400 ~ 450 DEG C of heating 1.0 ~ 2.0 hours, then 550 ~ 700 DEG C of heating 0.5 ~ 2.0 hour.
According to certain embodiments of the present invention, described Heating temperature 400 ~ 450 DEG C is such as 410 DEG C, 415 DEG C, 420 DEG C, 425 DEG C, 430 DEG C, 435 DEG C, 440 DEG C, 445 DEG C, 450 DEG C;
1.0 ~ 2.0 hours described heat-up times were such as 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2.0 hours;
Described Heating temperature 550 ~ 700 DEG C is such as 560 DEG C, 580 DEG C, 600 DEG C, 620 DEG C, 640 DEG C, 660 DEG C, 680 DEG C, 700 DEG C;
0.5 ~ 2.0 hour described heat-up time was such as: 0.6 hour, 0.8 hour, 1.0 hours, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2.0 hours.
In aforesaid method, also can a brometo de amonio for synthesis be recycled to recycle in step (1) in room temperature ~ 250 DEG C by step (2); Also the Ammonia recovery discharged can be utilized, thus reduce production cost, improve productivity.
Fig. 2 is shown in the technical process of anhydrous lanthanum bromide prepared according to the methods of the invention.
In addition, contriver also explores the reaction mechanism of the inventive method further by a large amount of experiments, and find, lanthanum trioxide and brometo de amonio react between 300 ~ 400 DEG C, generates the double salt XNH of lanthanum bromide and brometo de amonio 4brLaBr 3yH 2o.Double salt XNH 4brLaBr 3yH 2o hydrolysis degree in heat-processed is less; When temperature continues to raise, XNH 4brLaBr 3yH 2o discharges crystal water and brometo de amonio gradually, obtains anhydrous lanthanum bromide.The brometo de amonio discharged is decomposed into hydrogen bromide further and ammonia overflows, these gases can the concentration of water vapour and oxygen in diluting reactor, simultaneously brometo de amonio and hydrogen bromide can effectively in inhibited reaction device hydrolysis reaction generation and hydrolysate can be converted into anhydrous lanthanum bromide, thus ensure that the purity of anhydrous lanthanum bromide.
Therefore, in the method for the invention, the effect of brometo de amonio is: one, lanthanum trioxide is converted into corresponding bromide; Two, at a certain temperature brometo de amonio decompose the bromize hydrogen gas that produces and ammonia can the concentration of water vapour and oxygen in diluting reactor; Three, bromize hydrogen gas effectively can suppress the generation of anhydrous lanthanum bromide hydrolysis reaction; Four, the hydrolysate in reaction process all can be converted into anhydrous lanthanum bromide by brometo de amonio and hydrogen bromide, thus ensure that the purity of the anhydrous lanthanum bromide of product.The purity of anhydrous lanthanum bromide adopting the method for the invention to prepare is greater than 99.5%, water content is less than 0.1%.
Compared with the preparation method of existing anhydrous lanthanum bromide, the method for the invention possesses following advantage:
(1) utilize lanthanum trioxide and brometo de amonio to be raw material directly obtained anhydrous lanthanum bromide, these raw materials are easy to get, cost is lower;
(2) preparation technology of anhydrous lanthanum bromide is simple, flow process is short, and preparation process easily controls, and product yield is high, and production cost is low;
(3) purity of the anhydrous lanthanum bromide prepared by is high (purity reaches more than 99.5%, and water content is less than 0.1%).
Accompanying drawing explanation
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing:
Fig. 1 is the XRD figure spectrum of anhydrous lanthanum bromide prepared according to the methods of the invention;
Fig. 2 is the process flow sheet of anhydrous lanthanum bromide prepared according to the methods of the invention.
Embodiment
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows.
The embodiment of the present invention is tested prepared anhydrous lanthanum bromide according to following method:
1. titration measuring sample aqueous solution throw out is to determine the purity of anhydrous lanthanum bromide.
In the present invention, the major impurity in anhydrous lanthanum bromide is lanthanum oxybromide (LaOBr), and the method for calculation of anhydrous lanthanum bromide purity are: anhydrous lanthanum bromide purity=100%-LaOBr%; Wherein, LaOBr% refers to the weight percentage that lanthanum oxybromide is shared in the sample to which.The method measuring LaOBr% is as follows: by soluble in water for the anhydrous lanthanum bromide sample prepared, repeatedly filter three times with the quantitative paper (Hangzhou Special Paper Industry Co., Ltd.) of six Φ 90mm till filtrate is clarified especially to the aqueous solution.Filter paper deionized water is rinsed repeatedly wash away the lanthanum ion adhered to above, putting into beaker by washing the rear filter paper containing lanthanum oxybromide particle, adding hydrochloric acid (analytical pure, the purity 36% ~ 38% of the 1+1 of excessive preparation; Producer: Beijing Chemical Plant), solution heated and boiled in beaker also leaves standstill by electric furnace and throw out was reacted completely in five minutes.Solution in beaker is carried out EDTA titration to determine that the content of lanthanum ion (be shown in " nonferrous metallurgy analysis handbook " by testing method, metallurgical industry press, 2008, P330-331), thus obtain the content of lanthanum oxybromide in anhydrous lanthanum bromide, and then be converted into the purity of anhydrous lanthanum bromide.
2. the mensuration of moisture content in sample.
With the preparation-obtained sample of the inventive method because be incubated the long period at relatively high temperatures, free water or crystal water should not be contained in sample, even if having water also to react with anhydrous lanthanum bromide at such high temperatures generate lanthanum oxybromide, test the moisture that the moisture measured is all absorption of sample in mensuration process and in normal temperature preservation process.The mensuration of moisture adopts karl Fischer volumetry, and instrument adopts the KF-1B type moisture content tester of instrucment and meter plant of Shanghai Chemical Research Inst.
3.X x ray diffraction analysis x.
Use X-ray diffractometer (model: X'Pert PRO MPD; Producer: Philips) adopt X-ray diffraction (XRD) to determine the existence of anhydrous lanthanum bromide.
Raw material involved in the present invention is commercially available product, comprising:
Lanthanum trioxide: Chemical Reagent Co., Ltd., Sinopharm Group, purity >=99.99%;
Brometo de amonio: Xilong Chemical Co., Ltd, purity >=99.0%.
Aluminum oxide: Chemical Reagent Co., Ltd., Sinopharm Group, purity >=99.4%;
Quartz sand: Chemical Reagent Co., Ltd., Sinopharm Group, purity >=99.8%.
Repone K: Xilong Chemical Co., Ltd, purity >=99.5%;
Bariumchloride: Xilong Chemical Co., Ltd, purity >=99.0%;
Magnesium oxide: Chemical Reagent Co., Ltd., Sinopharm Group, purity >=98.5%;
Ammonium chloride: Xilong Chemical Co., Ltd, purity >=99.5%.
Porous ceramics: preparation method is shown in document in detail: Zhang Zhi, preparation and property research [Master's thesis] of high-temperature floamed ceramic, Chinese Academy Of Sciences Process Engineering Research Institute, 2010.5.
Embodiment 1
Add in corundum crucible after 6.52g lanthanum trioxide and 23.5g brometo de amonio are mixed.By mixture first 400 DEG C of insulations 2.0 hours, then 550 DEG C of insulations 1.0 hours.So just obtain anhydrous lanthanum bromide.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 3.60:1, and the mixture of lanthanum trioxide and brometo de amonio is coverture, and mantle thickness is 7mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3, see accompanying drawing 1.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.58%.
Measure moisture content in sample, recording moisture content in sample is 0.08%.
Embodiment 2
Add in corundum crucible after 3.26g lanthanum trioxide and 11.75g brometo de amonio are mixed.Then, aluminum oxide thick for 10mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 350 DEG C of insulations 2.0 hours, then 550 DEG C of insulations 1.0 hours.So just obtain the anhydrous lanthanum bromide of layering obvious upper strata aluminum oxide and lower floor.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 3.60:1, and aluminum oxide is coverture, and mantle thickness is 10mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.60%.
Measure moisture content in sample, recording moisture content in sample is 0.10%.
Embodiment 3
Add in corundum crucible after 13.04g lanthanum trioxide and 47.00g brometo de amonio are mixed.Then, aluminum oxide thick for 13mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 400 DEG C of insulations 2.5 hours, then 600 DEG C of insulations 1.0 hours.So just obtain the anhydrous lanthanum bromide of layering obvious upper strata aluminum oxide and lower floor.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 3.60:1, and aluminum oxide is coverture, and mantle thickness is 13mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.69%.
Measure moisture content in sample, recording moisture content in sample is 0.09%.
Embodiment 4
Add in corundum crucible after 3.26g lanthanum trioxide and 23.50g brometo de amonio are mixed.Then, aluminum oxide thick for 65mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 450 DEG C of insulations 1.5 hours, then 650 DEG C of insulations 0.8 hour.So just obtain the anhydrous lanthanum bromide of layering obvious upper strata aluminum oxide and lower floor.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 7.21:1, and aluminum oxide is coverture, and mantle thickness is 65mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.68%.
Measure moisture content in sample, recording moisture content in sample is 0.08%.
Embodiment 5
Add in corundum crucible after 3.26g lanthanum trioxide and 23.50g brometo de amonio are mixed.Then, quartz sand thick for 73mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 450 DEG C of insulations 1.5 hours, then 650 DEG C of insulations 0.8 hour.So just obtain the anhydrous lanthanum bromide of layering obvious upper strata quartz sand and lower floor.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 7.21:1, and quartz sand is coverture, and mantle thickness is 73mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.71%.
Measure moisture content in sample, recording moisture content in sample is 0.07%.
Embodiment 6
Add in corundum crucible after 3.26g lanthanum trioxide and 23.50g brometo de amonio are mixed.Then, aluminum oxide thick for 73mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 450 DEG C of insulations 1.5 hours, then 700 DEG C of insulations 0.4 hour.So just obtain the anhydrous lanthanum bromide of layering obvious upper strata aluminum oxide and lower floor.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 7.21:1, and aluminum oxide is coverture, and mantle thickness is 73mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.65%.
Measure moisture content in sample, recording moisture content in sample is 0.09%.
Embodiment 7
Add in corundum crucible after 3.26g lanthanum trioxide and 5.87g brometo de amonio are mixed.Then, aluminum oxide thick for 86mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 250 DEG C of insulations 4.0 hours, then 850 DEG C of insulations 0.5 hour.So just obtain the anhydrous lanthanum bromide of layering obvious upper strata aluminum oxide and lower floor.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 1.80:1, and aluminum oxide is coverture, and mantle thickness is 86mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.70%.
Measure moisture content in sample, recording moisture content in sample is 0.07%.
Embodiment 8
Add in corundum crucible after 3.26g lanthanum trioxide and 9.71g brometo de amonio are mixed.Then, aluminum oxide thick for 8mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 500 DEG C of insulations 1.0 hours, then 500 DEG C of insulations 3.0 hours.So just obtain the anhydrous lanthanum bromide of layering obvious upper strata aluminum oxide and lower floor.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 2.98:1, and aluminum oxide is coverture, and mantle thickness is 8mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.73%.
Measure moisture content in sample, recording moisture content in sample is 0.08%.
Embodiment 9
Add in corundum crucible after 3.26g lanthanum trioxide and 47.07g brometo de amonio are mixed.Then, aluminum oxide thick for 4mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 400 DEG C of insulations 2.0 hours, then 700 DEG C of insulations 0.5 hour.So just obtain the anhydrous lanthanum bromide of layering obvious upper strata aluminum oxide and lower floor.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 14.44:1, and aluminum oxide is coverture, and mantle thickness is 4mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.80%.
Measure moisture content in sample, recording moisture content in sample is 0.06%.
Embodiment 10
Add in corundum crucible after 3.26g lanthanum trioxide and 47.07g brometo de amonio are mixed.By mixture first 450 DEG C of insulations 1.0 hours, then 550 DEG C of insulations 2.0 hours.So just obtain anhydrous lanthanum bromide.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 14.44:1, and the mixture of lanthanum trioxide and brometo de amonio is coverture, and mantle thickness is 8mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.83%.
Measure moisture content in sample, recording moisture content in sample is 0.06%.
Can be seen by the result of above embodiment, in the anhydrous lanthanum bromide prepared by the method utilizing lanthanum trioxide to prepare anhydrous lanthanum bromide according to the present invention, can by the control of purity of anhydrous lanthanum bromide more than 99.5%, water-content controls within 0.1%.
Embodiment 11
Add in corundum crucible after 3.26g lanthanum trioxide and 9.71g brometo de amonio are mixed.Then, the mixture of aluminum oxide thick for 10mm and quartz sand is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 400 DEG C of insulations 1.0 hours, then 550 DEG C of insulations 1.0 hours.So just obtain anhydrous lanthanum bromide.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 2.98:1, and the mixture of aluminum oxide and quartz sand is coverture, and mantle thickness is 10mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.85%.
Measure moisture content in sample, recording moisture content in sample is 0.04%.
Embodiment 12
Add in corundum crucible after 3.26g lanthanum trioxide and 9.71g brometo de amonio are mixed.Then, the mixture of magnesium oxide thick for 10mm and ammonium chloride is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 400 DEG C of insulations 1.0 hours, then 550 DEG C of insulations 1.0 hours.So just obtain anhydrous lanthanum bromide.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 2.98:1, and the mixture of magnesium oxide and ammonium chloride is coverture, and mantle thickness is 10mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.76%.
Measure moisture content in sample, recording moisture content in sample is 0.08%.
Embodiment 13
Add in corundum crucible after 3.26g lanthanum trioxide and 9.71g brometo de amonio are mixed.Then, Repone K thick for 10mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 400 DEG C of insulations 1.0 hours, then 550 DEG C of insulations 1.0 hours.So just obtain anhydrous lanthanum bromide.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 2.98:1, and Repone K is coverture, and mantle thickness is 10mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.88%.
Measure moisture content in sample, recording moisture content in sample is 0.05%.
Embodiment 14
Add in corundum crucible after 3.26g lanthanum trioxide and 9.71g brometo de amonio are mixed.Then, bariumchloride thick for 10mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 400 DEG C of insulations 1.0 hours, then 550 DEG C of insulations 1.0 hours.So just obtain anhydrous lanthanum bromide.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 2.98:1, and bariumchloride is coverture, and mantle thickness is 10mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.82%.
Measure moisture content in sample, recording moisture content in sample is 0.09%.
Embodiment 15
Add in corundum crucible after 3.26g lanthanum trioxide and 9.71g brometo de amonio are mixed.Then, porous ceramics thick for 12mm is covered on the mixture of lanthanum trioxide and brometo de amonio.By mixture first 400 DEG C of insulations 1.0 hours, then 550 DEG C of insulations 1.0 hours.So just obtain anhydrous lanthanum bromide.In this embodiment, the mass ratio of brometo de amonio and lanthanum trioxide is 2.98:1, and porous ceramics is coverture, and mantle thickness is 12mm.
Characterize the anhydrous lanthanum bromide obtained according to above-mentioned measuring method, its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous LaBr 3.
Throw out after water-soluble to sample carries out titration, and the purity recording anhydrous lanthanum bromide is 99.73%.
Measure moisture content in sample, recording moisture content in sample is 0.06%.
Can be seen by the result of above embodiment, in the anhydrous lanthanum bromide prepared by the method utilizing lanthanum trioxide to prepare anhydrous lanthanum bromide according to the present invention, can by the control of purity of anhydrous lanthanum bromide more than 99.5%, water-content controls within 0.1%.
Above provide specific descriptions of the present invention for setting forth and illustrating.But do not really want exhaustive or limit the invention to disclosed precise forms.According to above instruction, a lot of amendment and modification can be realized.Above-described embodiment is selected for explaining principle of the present invention and practical application thereof best, thus makes those skilled in the art the different modification being suitable for certain expected purposes also can be utilized to utilize the present invention best with different embodiments.Scope of the present invention will be defined by claims.

Claims (7)

1. prepare a method for anhydrous lanthanum bromide, comprise the steps:
(1) by brometo de amonio and lanthanum trioxide Homogeneous phase mixing;
(2) step (1) gained mixture is heated under the closed environment with certain stopping property, obtain anhydrous lanthanum bromide.
2. method according to claim 1, is characterized in that, described in step (1), the mass ratio of brometo de amonio and lanthanum trioxide is greater than 1.80; Preferably, the mass ratio of described brometo de amonio and lanthanum trioxide is 1.80 ~ 36.10:1.00; Further preferably, the mass ratio of described brometo de amonio and lanthanum trioxide is 2.98 ~ 14.44:1.00.
3. method according to claim 1 and 2, is characterized in that, in step (2), realizes described closed environment by placing coverture on described mixture; Preferably, described coverture is solid powder or porous material; Further preferably, described solid powder is any one or a few mixture of Repone K, sodium-chlor, bariumchloride, calcium chloride, aluminum oxide, quartz sand, magnesium oxide, lanthanum trioxide, brometo de amonio, ammonium chloride, and described porous material is ceramic porous material, silicon carbide porous material, silicon oxide porous material, silico-aluminate porous material, aluminum oxide porous material, titanium oxide porous material, zirconium white porous material, manganese oxide porous material, ferric oxide multi-porous material, phosphate cellular material, sulfide porous material.
4. method according to claim 3, is characterized in that, the thickness of described coverture is greater than 4mm; Preferably, the thickness of described coverture is greater than 8mm.
5. the method according to any one of claim 1-4, is characterized in that, step is heated to be described in (2): first 250 ~ 500 DEG C of heating 1.0 ~ 4.0 hours, then 500 ~ 850 DEG C of heating 0.5 ~ 3.0 hour.
6. method according to claim 5, is characterized in that, step is heated to be described in (2): first 400 ~ 450 DEG C of heating 1.0 ~ 2.0 hours, then 550 ~ 700 DEG C of heating 0.5 ~ 2.0 hour.
7. the method according to any one of claim 1-6, is characterized in that, by step (2), in room temperature ~ 250, the brometo de amonio of DEG C synthesis is recycled to recycle in step (1).
CN201310376639.5A 2013-08-26 A kind of preparation method of anhydrous lanthanum bromide Active CN104418379B (en)

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Publication number Priority date Publication date Assignee Title
CN107021519A (en) * 2017-03-23 2017-08-08 上海新漫晶体材料科技有限公司 A kind of preparation method of high-pure anhydrous lanthanum bromide powder
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CN111186853A (en) * 2018-10-26 2020-05-22 北京梦晖科技有限公司 Preparation method of rare earth halide
CN110092405A (en) * 2019-04-26 2019-08-06 兰州大学 A kind of preparation method of anhydrous rare earth bromide
CN111468146A (en) * 2020-05-09 2020-07-31 中国科学院上海硅酸盐研究所 Rare earth bromine oxide photocatalytic material and preparation method and application thereof
CN111468146B (en) * 2020-05-09 2023-01-31 中国科学院上海硅酸盐研究所 Rare earth bromine oxide photocatalytic material and preparation method and application thereof
CN112010339A (en) * 2020-09-04 2020-12-01 内蒙古蒙稀新材料有限责任公司 Preparation method of high-purity anhydrous rare earth chloride
CN112010339B (en) * 2020-09-04 2021-06-18 内蒙古蒙稀新材料有限责任公司 Preparation method of high-purity anhydrous rare earth chloride
CN113072090A (en) * 2021-04-23 2021-07-06 中国恩菲工程技术有限公司 Preparation method of anhydrous scandium chloride molten salt

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